Layer member forming method

ABSTRACT

A vapor reaction method including the steps of providing a pair of first and second electrodes within a reaction chamber where the pair of electrodes are arranged substantially parallel with each other. The method further includes the steps of placing a substrate in the reaction chamber where the substrate is held by said first electrode so that a first surface of the substrate faces toward the second electrode. A first film forming gas is introduced into the reaction chamber through the second electrode. The first film forming gas is excited to form a first insulating film by vapor deposition. The first insulating film may be silicon nitride. The method may also include the step of introducing a second film forming gas into the reaction chamber through the second electrode to ultimately form a second film. After removing the substrate from the reaction chamber, a cleaning gas may then be introduced through the second electrode to remove unnecessary layers from the inside of the reaction chamber.

This application is a DIV of Ser. No. 08/659,636 Jun. 6, 1996 ABN whichis a DIV of Ser. No. 08/351,140 Nov. 30, 1994 U.S. Pat. No. 5,650,013which is a CON of Ser. No. 08/064,212 May 12, 1993 ABN which is a DIV ofSer. No. 07/842,758 Feb. 28, 1992 ABN which is a CON of Ser. No.07/595,762 Oct. 3, 1990 ABN which is a CON of Ser. No. 07/312,420 Feb.21, 1989 ABN which is a CON of Ser. No. 07/092,130 Sep. 2, 1987 ABNwhich is a DIV of Ser. No. 06/801,768 Nov. 26, 1985 ABN.

BACKGROUND OF THE INVENTION

1. Field of the Invention

The present invention relates to a layer member forming method which issuitable for use in the fabrication of various electronic devices of thetype having an insulating, protecting, conductive, semiconductor or likelayer member formed on a substrate member.

2. Description of the Prior Art

Heretofore there has proposed a method for forming such a layer memberon a substrate member through use of a photo CVD or plasma CVD process.

According to the method utilizing the photo CVD technique, the substrateis placed in a reaction chamber provided with a light transparent windowand a reactive gas mixture, which contains at least a gas of a materialfor the formation of the layer member desired to obtain, is introducedinto the reaction chamber. Then light is introduced into the reactionchamber through the light transparent window thereof by which thereactive gas mixture introduced thereinto is excited for vapor-phasedecomposition and the material for the layer is deposited on thesubstrate member.

With the method utilizing the plasma CVD technique, the substrate isplaced in a reaction chamber and a reactive gas mixture, which containsa gas of a material for the formation of the layer, is introduced intothe reaction chamber. In the reaction chamber the reactive gas mixtureis excited into a plasma by grow discharge or electron cyclotronresonance for vapor-phase decomposition by high frequency electric powerso that the material for the layer is deposited on the substrate.

With the photo CVD process, since the material gas resulting from thevapor-phase decomposition of the photo-excited reactive gas is notaccelerated, it is possible to form the layer on the substrate withsubstantially no damage inflicted on the substrate surface. On thisaccount the layer can easily be formed without containing the materialforming the substrate surface or without introducing into the substratesurface the material forming the layer, without developing anyundesirable interface level between the layer and the substrate andwithout applying any internal stress to the layer and the substrate.Furthermore, since the photo-excited material gas has a characteristicto spread on the surface of the substrate member, the layer can bedeposited in close contact with the substrate even if the substratesurface is uneven.

Accordingly, the use of the photo CVD technique permits easy formationof the layer of desired characteristics, without causing any damages tothe substrate surface, even if the substrate has an uneven surface.

With the photo CVD process, however, since the photo-excited materialgas is not accelerated toward the substrate, the deposition rate of thelayer is lower than in the case of employing the plasma CVD technique.Therefore, the photo CVD process takes much time for forming the layeras compared with the plasma CVD process. Furthermore, the material forthe layer is deposited as well on the light transparent window duringthe formation of the layer, causing a decrease in the lighttransmittivity of the window as the deposition proceeds. Therefore, thelayer cannot be formed to a large thickness. For instance, in the caseof forming a silicon nitride layer, it is difficult, in practice, todeposit the layer to a thickness greater than 1000 A. Moreover,difficulties are encountered in forming a silicon layer to a thicknessgreater than 200 A, a silicon oxide (SiO₂), or aluminum nitride (AlN)layer to a thickness greater than 3000 A, a silicon carbide (Si_(xC)_(1-x) , where 0<x<1) layer to a thickness greater than 500 A and agermanium silicide (Si_(x)Ge_(1-x), where 0<x <1) or metal silicide(SiM_(x), where M is metal such as Mo, W, In, Cr, Sn Ga or the like and0<X≦4) layer to a thickness greater than 100 to 200 A.

with the plasma CVD process, since the material gas resulting from thevapor decomposition of the reactive gas excited by electric power can beaccelerated toward the substrate, the deposition rate of the layer ishigher than in the case of using the photo CVD process. Therefore, thelayer can be formed on the substrate in a shorter time than is needed bythe photo CVD technique. Furthermore, even if the material for the layeris deposited on the interior surface of the reaction chamber as well ason the substrate, no limitations are imposed on the excitation of thereactive gas by electric power. Consequently, the layer can easily beformed to a desired thickness on the substrate.

With the plasma CVD technique, however, since the material gas excitedby electric power is accelerated by an electric field, it is difficultto deposit the layer on the substrate without causing damage to itssurface. On account of this, the layer contains the material forming thesubstrate surface, or the substrate surface contains the materialforming the layer. Moreover, an interface level is set up between thelayer and the substrate and internal stresses are applied to the layerand the substrate.

Besides, in the case of employing the plasma CVD technique, since theexcited material gas is accelerated by an electric field and its freerunning In the reaction chamber is limited, there is the possibilitythat when the substrate surface is uneven, the layer cannot be formed inclose contact therewith, that is, the layer cannot be deposited withdesired characteristics.

SUMMARY OF THE INVENTION

It is therefore an object of the present invention to provide a novellayer member forming method which is free from the abovesaid defects ofthe prior art.

The layer member forming method of the present invention comprises thesteps of depositing a layer of a desired material on a substrate by thephoto CVD technique and depositing on the first layer a second layer ofa material identical with or different from that of first layer by theplasma CVD technique, thereby forming a layer member composed of atleast the first and second layers.

According to such a method of the present invention, since the firstlayer is deposited by the photo CVD technique on the substrate, even ifthe substrate surface is uneven, the first layer can be deposited inclose contact with the substrate surface and with substantially nodamage thereon. Accordingly, the first layer does not substantiallycontain the material forming the substrate surface, or the substratesurface does not substantially contain the material forming the firstlayer. Further, the deposition of the first layer is not accompanied byprovision of an undesirable interface level between the first layer andthe substrate and the application of internal stresses to the firstlayer and the substrate. In addition, since the second layer isdeposited by the plasma CVD technique on the first layer, the secondlayer can easily be formed to a desired thickness in a short time.

In accordance with an aspect of the present invention, by forming thefirst and second layers as insulating, protecting or conductive layersof the same or different types or compositions, the layer member as ainsulating, protecting or conductive layer member of desiredcharacteristics can easily be deposited to desired thickness in a shorttime without inflicting damage on the substrate surface.

In accordance with another aspect of the present invention, by formingthe first and second layers as semiconductive layers of the same type orcomposition, the layer member as a semiconductor layer member can easilybe deposited to a desired thickness in a short time without inflictingdamage to the substrate surface.

In accordance with another aspect of the present invention, by formingthe first and second layers as semiconductor layers of different typesor compositions, the layer member can easily be deposited as asemiconductor layer member composed of a first semiconductor layer whichmay preferably be relatively thin and a second semiconductor layer whichmay preferably be relatively thick, in a short time without causingdamage to the substrate surface.

In accordance with another aspect of the present invention, by formingthe first and second layers as an insulating layers and as a conductiveor semiconductor layer, respectively, the layer member as a compositelayer member can easily be deposited including a conductive orsemiconductor layer formed to a desired thickness on the insulatinglayer of the least possible thickness, in a short time without impairingthe substrate surface.

In accordance with yet another aspect of the present invention, byforming the first and second layers as a conductive or semiconductorlayer and as an insulating or protecting layer, respectively, the layermember as a composite layer member can easily be deposited including aninsulating or protecting layer formed to a desired thickness on theconductive or semiconductive layer of the least possible thickness, in ashort time without impairing the substrate surface.

Other objects, features and advantages of the present invention willbecome more fully apparent from the following description taken inconjunction with the accompanying drawings.

BRIEF DESCRIPTION OF THE DRAWING

The accompanying sheet of a drawing schematically illustrates an exampleof the layer forming method of the present invention and an example ofapparatus used therefor.

DESCRIPTION OF THE PREFERRED EMBODIMENTS

A description will be given first of an apparatus for the formation of alayer member according to the present invention.

The apparatus has a conductive reaction chamber 10. The reaction chamber10 is provided with a plurality of conductive nozzles 11 arranged at thelower portion of the chamber 10 and each having upper and lower nozzleparts 12 a and 12 b. The conductive nozzles 11 are connected to one endof a power supply 15 for gas excitation.

A gas introducing pipe 13 is connected to the upper nozzle parts 12 a ofthe nozzle 11 and extends out of the reaction chamber 10. The gasintroducing pipe 13 is connected to a gas source 14A via a valve 15A anda flowmeter 16A and to another gas source 14B via a valve 15B and aflowmeter 16B.

Another gas introducing pipe 17 is connected to the lower nozzle parts12 b of the nozzle 11 and extends out of the reaction chamber 10. Thegas introducing pipe 17 is connected to a gas source 18A via a valve 18Aand a flowmeter 20A, to a gas source 18B via a valve 19B and a flowmeter20B and to a gas source 18C via a valve 19C and a flowmeter 20C.

The reaction chamber 10 is provided with an exhaust pipe 21 whichextends to the outside through the bottom wall of its extending portion10′ wherein the nozzles 11 are not placed. The exhaust pipe 21 isconnected to a vacuum pump system 22 via a control valve 23 and achange-over valve 24. The vacuum pump system 22 has a tandem structureof a turbo pump 25 and a rotary pump 26.

Provided on the bottom wall of the reaction chamber 10 is a light sourcechamber 30, in which is disposed light sources 31 each of which emitslight having a wavelength 300 nm or less, such as a low pressure mercurylamp. The light sources 31 are connected to an external power supply(not shown). Provided on the bottom wall of the chamber 30 are coolingpipes 51 which are connected to a cooling tower (not shown).

The reaction chamber 10 and the light source chamber 30 opticallyintercommunicate through a window 33 made in, for instance, a quartzplate disposed therebetween.

The light source chamber 30 has a gas introducing pipe 34 which extendsto the outside through its one end portion of the bottom wall. The gasintroducing pipe 34 is connected to a gas source 35 via a valve 36 andfolwmeter 37. The light source chamber 30 has an exhaust pipe 38 whichextends from the other end portion of the bottom wall of the chamber 30into the extending portion 10′ of the reaction chamber 10. A heater 39is provided on the exhaust pipe 38.

Disposed on the upper wall of the reaction chamber 10 is a heat sourcechamber 40, in which is disposed a heat source 41 formed by, forexample, a halogen lamp. The heat source 41 is connected to an externalpower supply (not shown). Provided on the top wall of the chamber 40 iscosting pipes 61 which are connected to the abovesaid costing tower.

The reaction chamber 10 and the heat source chamber 40 thermallyintercommunicate through a window 43 made in, for example, quartz platedisposed there between.

The light source chamber 40 has a gas introducing pipe 44 which extendsthrough its one end portion of the upper wall to the outside and isconnected to abovesaid gas source 35 via the valve 36 and the flowmeter37. The heat source chamber 40 has an exhaust pipe 48 which extends fromits other end portion of the upper wall into the extending portion 10′of the reaction chamber 10. A heater 49 is provided on the exhaust pipe48.

The reaction chamber 10 has attached thereto on the side of itsextending portion 10′ a substrate take-in/take-out chamber 70 with ashutter means 71 interposed therebetween. The shutter means 71 isselectively displaced to permit or inhibit the intercommunicationtherethrough between the chambers 10 and 70.

The chamber 70 has another shutter means 72 on the opposite side fromthe shutter means 71. The chamber 70 has an exhaust pipe 73 whichextends from its bottom to the vacuum system 22 via the aforementionedchange-over valve 24. The chamber 70 has another pipe 75 which extendsto the outside and terminates into the atmosphere via a valve 76.

The apparatus includes a conductive holder 81 for mounting a pluralityof substrate members 90. The holder 81 is combined with thermallyconductive press plates 82 for placing on the substrate members 90mounted on the holder 81.

According to an example of the present invention, the abovesaid layermember is deposited on the substrate member 90 through use of such anapparatus, as described hereinafter.

Embodiment 1

A description will given of a first embodiment of the present inventionfor forming the layer member as a insulating layer member on thesubstrate member 90.

(1) The shutter means 71 between the reaction chamber 10 and thesubstrate take-in/take-out chamber 70, the shutter means 72 of thechamber 70 a valve 76 between the chamber 70 and the outside, the valves15A and 15B between the nozzle parts 12 a and the gas sources 14A and14B, the valve 19A, 19B and 19C between the nozzle parts 12 b and thegas sources 18A, 18B and 18C and the valve 36 between the chambers 30and 40 and the gas source 35 are closed.

(2) Next, the valve 23 between the reaction chamber 10 and the vacuumpump system 22 is opened and change-over valve 24 is also opened to theboth chambers 10, 70, 30 and 40 to a pressure of 10⁻⁷ Torr.

(3) Next, the turbo pump 25 and the rotary pump 26 of the vacuum pumpsystem 22 are activated, evacuating the chambers 10 and 70.

(4) Next, the valve 23 is closed and the change-over valve 24 is alsoclosed relative to the both chambers 10 and 70, followed by stopping ofthe vacuum pump system 22 from operation.

(5) Next, the valve 76 is opened, raising the pressure in the chamber 70up to the atmospheric pressure.

(6) Next, the shutter means 72 is opened, through which the substrate 90mounted on a holder 81 with, its surface for the formation thereon ofthe layer held down, is placed in the chamber 70 with a press plate 82mounted on the substrate 90.

(7) Next, the shutter means 72 and the valve 76 are closed.

(8) Next, the change-over valve 24 is opened to the chamber 70 alone andthe pump system 22 is activated, evacuating the chamber 70 tosubstantially the same vacuum as that in which the chamber 10 isretained.

(9) Next, the change-over valve 24 is closed relative to the bothchambers 10 and 70 and then the pump system 22 is stopped fromoperation.

(10) Next, the shutter means 71 is opened, the holder 81 carrying thesubstrate 90 is moved from the chamber 70 into the chamber 10 anddisposed at a predetermined position in the upper part of the chamber10. At this time, the holder 81 is connected to the other end of thepower source 15.

(11) Next, the shutter means 71 is closed.

(12) Next, the heat source 41 in the heat source chamber 40 is turnedON, heating the substrate 90 up to a temperature of 350° C.

(13) Next, the light source 31 in the light source chamber 30 is turnedON.

(14) Next, the valve 19A connected to the lower nozzle part 12 b of thenozzle 11 in the reaction chamber 10 is opened, through which ammoniagas (NH₃) is introduced as a first reactive material gas from the gassource 18A into the chamber 10. At the same time, the valve 23 is openedand the valve 24 is opened relative to the chamber 10 alone and,further, the pump system 22 is activated, raising the pressure in thechamber 10 to 3 Torr. Then the valve 15B connected to the upper nozzleparts 12 a of the nozzle 11 is opened, through which disilane (Si₂H₆) isintroduced as a second reactive material ga from the gas source 14B intothe chamber 10 to provide therein a gas mixture of the ammonia gas andthe disilane. The pressure in the chamber 10 is held at 3 Torr byregulating the valve 23. In this instance, exhaust pipes 38 and 48between the chambers 30 and 40 and the reaction chamber 10 are heated byheaters 39 and 49 mounted thereon, respectively. Even if the gas mixtureflows back from the reaction chamber 10 in the pipes 38 and 48 towardthe chambers 30 and 40, it is vapor-decomposed by heat to depositsilicon nitride and silicon on the interior surfaces of the pipes 38 and48, preventing the silicon nitride and silicon from deposition on theinside surfaces of the chambers 30 and 40. Furthermore, in order toprevent such a reverse flowing of the gas mixture, the valve 36 isopened, through which nitrogen or argon gas is introduced from the gassource 35 into the chambers 30 and 40.

In such a condition, the gas mixture is excited by light from the lightsource 31 desposed in the light source chamber 31, by which it isexcited and vapor-decomposed, depositing a first silicon nitride layeras a first insulating layer on the substrate 90 at a rate of 17 A/min.

(15) Next, when the first silicon nitride layer is deposited to athickness of about 500 A on the substrate 90, the valve 23 is regulatedand when the pressure in the chamber 10 is reduced to 1 Torr, the powersource 15 is turned ON and then the light source 31 is turned OFF.

In such a condition, the gas mixture of the ammonia gas and the disilaneis discharged or excited by electric power from the power source 15 intoa plasma, in consequence of which a second silicon nitride layer isdeposited as a second insulating layer on the first silicon nitridelayer at a rate 2.1 A/sec.

(16) Next, when the second silicon nitride layer is deposited to athickness of about 0.5 μm, the power source 15 is turned OFF and thenthe valves 15B 19A and 36 are closed but the valve 23 is fully opened,evacuating the chambers 10 and 30 to the same degree of vacuum as thatunder which the chamber 70 is held.

(17) Next, the valve 23 is closed and the pump system 22 is stopped andthen the shutter means 71 is opened, through which the holder 81carrying the substrate member 90 with the first and second insulatinglayers deposited thereon in this order is moved from the chamber 10 tothe chamber 70.

(18) Next, the shutter means 71 is closed and then the valve 76 isopened, through which the pressure in the chamber 70 is raised to theatmospheric pressure.

(19) Next, the shutter means 72 is opened, through which the holder 81is taken out to the outside and then the substrate member 90 havingformed thereon the first and second insulating layers is removed fromthe holder 81.

In the manner described above, the insulating layer member as the layermember is formed on the substrate 90.

(20) Next, the holder 81 with no substrate member 90 mounted thereon isplaced in the chamber 70, after which the shutter means 72 and the valve76 are closed, the valve 24 is opened to the chamber 70 and the vacuumpump system 22 is put in operation, evacuating the chamber 70 to thesame degree of vacuum as that under which the chamber 10 is retained.

(21) Next, the valve 24 is closed relative to the both chambers 70 and10, after which the shutter means 71 is opened, through which the holder81 is placed in the chamber 10, and then the shutter means 71 is closed.

(22) Next, the valve 19B connected to the lower nozzle parts 12 b of thenozzle 11 is opened, through which nitrogen fluoride (NF₃) is introducedas a first cleaning gas form the gas source 18B into the chamber 10. Onthe other hand, the valve 23 is opened and the valve 24 is opened to thechamber 10 and then the pump system 22 is put in operation, holding thepressure in the chamber 10 at 0.1 Torr.

(23) Next, the power source 15 is turned ON.

In such a condition, the first cleaning gas is discharged or excitedinto a plasma by electric power from the power source 15, etching awayunnecessary layers deposited on the inside surface of the chamber 10,the inside surfaces of the windows 33 and 34, the outside surface of thenozzle 11 and the outside surface of the holder 81. The unnecessarylayers are composed of the materials of abovesaid first and secondinsulating layer.

(24) Next, when the unnecessary layers are almost etched away, the powersource 15 is turned OFF and the valve 19B is closed, but the valve 19Cis opened, through which hydrogen as a second cleaning gas, suppliedfrom the gas source 18C, is introduced into the chamber 10, maintainingthe pressure therein at 0.1 Torr.

(25) Next, the power source 15 is turned ON again. The second cleaninggas is discharged or excited into a plasma by electric power from thepower source 15, cleaning the interior of the reaction chamber 10including the windows 33 and 34, the nozzles 11 and the holder 81.

(26) Next, the power source 15 is turned OFF, after which the valve 19Cis closed and the valve 23 is fully opened, through which the chamber 10is evacuated. When the chamber 10 is evacuated to the same degree ofvacuum as that under which the chamber 70 is retained, the valve 23 isclosed, stopping the pump system 22 from operation.

Thus a series of steps for forming an insulating layer member as a layermember on a substrate is completed.

Embodiment 2

Next, a description will be given of a second embodiment of the presentinvention for forming a semiconductor layer member as a layer member ona substrate.

This embodiment forms an amorphous silicon layer as the semiconductorlayer member on the substrate 90 by the same steps as those inEmbodiment 1 except the following steps.

(12′) In step (12) in Embodiment 1 the heating temperature of thesubstrate 90 is changed from 350 C to 250 C.

(14′) In step (14) of Embodiment 1 only the disilane (Si₂H₆) gas isintroduced into the chamber 10 and the pressure in the chamber 10 ischanged from 3 Torr to 2.5 Torr. A first amorphous silicon layer isdeposited as a first semiconductor layer on the substrate 90.

(15′) In step (15) of Embodiment 1, when the first amorphous siliconlayer, instead of the first silicon nitride layer, is deposited about1000 A thick on the substrate member 90, the disilane is discharged orexcited into a plasma in place of the gas mixture of the ammonia anddisilane, by which a second amorphous silicon layer is deposited as asecond semiconductor layer on the first amorphous silicon layer.

(16′) In step (16) of Embodiment 1, when the second amorphous siliconlayer, instead of the silicon nitride layer, is deposited about 1000 A,the power source 15 is turned OFF.

Embodiment 3

Next, a description will be given of a third embodiment of the presentinvention which forms an aluminum nitride (AlN) layer member as ainsulating layer member on a substrate.

Embodiment 3 employs a same steps as those in Embodiment 1 except thefollowing steps.

(14′) In step (14) of Embodiment 1 methyl aluminum (Al(CH₃)₃), insteadof the disilane, is introduced from the gas source 14A into the chamber10, whereby a first aluminum nitride (AlN) layer is deposited as a firstinsulating layer on the substrate 90. In this case, the deposition rateof the first aluminum nitride layer is 230 A/min.

(15′) In step (15) of Embodiment 1 a second aluminum nitride layer,instead of the second silicon nitride layer, is deposited on the firstaluminum nitride layer.

While in the foregoing the present invention has been described inconnection with the cases of forming an insulating layer member havingtwo insulating layers of the same material and a semiconductor layermember having two semiconductor layers of the same material, it is alsopossible to form an insulating layer member which has two insulating orprotecting layers of different materials selected from a groupconsisting of, for example, Si₃N₄, SiO₂, phosphate glass, borosilicateglass, and aluminum nitride. Also it is possible that an insulating orprotecting layer of, for instance, the abovesaid insulating orprotecting material and a conductive layer of such a metal as aluminum,iron, nickel or cobalt are formed in this order or in the reverse orderto form a composite layer member. Furthermore, a semiconductor layer ofa material selected from the group consisting of, for example, Si, Si_(x)C_(1-x) (where 0<x<1), SiM_(x) (where 0<x<4 and M is such a metal asMo, W, In, Cr, Sn or Ga) and the abovesaid insulating or protecting orconductive layer can also be formed in this order or in the reverseorder to obtain a composite layer member. Moreover, although in theforegoing a low pressure mercury lamp is employed as the light source,an excimer laser (of a wavelength 100 to 400 nm), an argon laser and anitrogen laser can also be used.

It will be apparent that many modifications and variations may beeffected with out departing from the scope of the novel concepts of thepresent invention.

1. A vapor reaction method comprising the steps of: providing a pair offirst and second electrodes within a reaction chamber, said pair ofelectrodes being arranged substantially in parallel with each other;placing a substrate in the reaction chamber wherein said substrate isheld by said first electrode so that a first surface of said substratefaces toward said second electrode; introducing a first film forming gasinto said reaction chamber through said second electrode; exciting saidfirst film forming gas in order to form a first insulating film by firstvapor deposition on said substrate placed in said reaction chamberwherein said first insulating film comprises silicon nitride;introducing a second film forming gas into said reaction chamber throughsaid second electrode; exciting said second film forming gas in order toform a second insulating film by a second vapor deposition directly onsaid first insulating film in said reaction chamber wherein said firstand second insulating films contact each other; removing said substratefrom said reaction chamber after the formation of the first and secondinsulating films; introducing a cleaning gas comprising nitrogenfluoride into said reaction chamber through said second electrode;exciting said cleaning gas in order to remove unnecessary layers causedthe first and second vapor depositions from an inside of the reactionchamber, wherein the second insulating film comprises a differentmaterial from the first insulating film.
 2. The vapor reaction methodaccording to claim 1 wherein said first vapor deposition is a photo CVD.3. The vapor reaction method according to claim 1 wherein said secondvapor deposition is a plasma CVD.
 4. The vapor reaction method accordingto claim 1 wherein said second electrode is provided with a plurality ofports for introducing said cleaning gas into the reaction chamber.
 5. Avapor reaction method comprising the steps of: providing a pair of firstand second electrodes within a reaction chamber, said pair of electrodesbeing arranged substantially in parallel with each other; placing asubstrate in a reaction chamber on said first electrode so that a firstsurface of said substrate faces toward said second electrode;introducing a first film forming gas into said reaction chamber throughsaid second electrode; exciting said first film forming gas in order toform a first film comprising silicon nitride by vapor deposition on saidsubstrate placed in said reaction chamber; introducing a second filmforming gas into said reaction chamber through said second electrode;exciting said second film forming gas in order to form a second film byvapor deposition directly on said first film in said reaction chamber;removing said substrate from said reaction chamber after the formationof the first and second films; introducing a cleaning gas comprisingnitrogen fluoride into said reaction chamber through said secondelectrode; exciting said cleaning gas in order to remove unnecessarylayers formed on an inside of the reaction chamber due to the formationof the first and second films.
 6. The vapor reaction method according toclaim 5 wherein said first vapor deposition is a photo CVD.
 7. A methodaccording to claim 5 wherein said second vapor deposition is a plasmaCVD.
 8. A method according to claim 5 wherein said second electrode isprovided with a plurality of ports for introducing said cleaning gasinto the reaction chamber.
 9. A method of fabricating electronic devicescomprising the steps of: providing a pair of electrodes within areaction chamber wherein said pair of electrodes are opposed in parallelwith each other; placing a substrate in a reaction chamber wherein saidsubstrate is placed on said pair of electrodes so that a first surfaceof said substrate faces toward said second electrode; introducing afirst film forming gas into said reaction chamber through the other oneof said electrodes; exciting said first film forming gas to form a firstfilm comprising silicon nitride by first chemical vapor deposition onsaid substrate; introducing a second film forming gas into said reactionchamber through the other one of said electrodes; exciting said secondfilm forming gas to form a second film by second chemical vapordeposition directly on said first film, said second film comprising adifferent material from said first film; removing said substrate fromsaid reaction chamber after the formation of said first and secondfilms; introducing a cleaning gas comprising nitrogen fluoride into saidreaction chamber through said other one of the electrodes; andconducting a cleaning of an inside of said reaction chamber by usingsaid cleaning gas to remove layers caused by at least said first andsecond vapor phase deposition.
 10. The method according to claim 9wherein said first chemical vapor deposition is a photo CVD.
 11. Themethod according to claim 9 wherein said second chemical vapordeposition is a plasma CVD.
 12. The method according to claim 9 whereinsaid cleaning gas is excited by said pair of electrodes.
 13. The methodaccording to claim 9 wherein said other one of the electrodes isprovided with a plurality of ports for introducing said cleaning gasinto the reaction chamber.
 14. A method of fabricating electronicdevices comprising the steps of: providing a pair of electrodes within areaction chamber wherein said pair of electrodes are opposed in parallelwith each other; placing a substrate in a reaction chamber wherein saidsubstrate is held by one of said electrodes so that a first surface ofsaid substrate faces toward said second electrode; introducing a firstfilm forming gas into said reaction chamber through the other one ofsaid electrodes; exciting said first film forming gas to form a firstfilm comprising silicon nitride by first chemical vapor deposition onsaid substrate; introducing a second film forming gas into said reactionchamber through the other one of said electrodes; exciting said secondfilm forming gas to form a second film by second chemical vapordeposition directly on said first film wherein said second filmcomprises a different material from said first film; removing saidsubstrate from said reaction chamber after the formation of said firstand second films; introducing a cleaning gas comprising nitrogenfluoride into said reaction chamber through said other one of theelectrodes; and conducting a cleaning of an inside of said reactionchamber by using said cleaning gas to remove layers caused by at leastsaid first and second vapor phase deposition, wherein one of the firstand second films comprises silicon nitride.
 15. The method according toclaim 14 wherein said first chemical vapor deposition is a photo CVD.16. The method according to claim 14 wherein said second chemical vapordeposition is a plasma CVD.
 17. The method according to claim 14 whereinsaid cleaning gas is excited by said pair of electrodes.
 18. The methodaccording to claim 14 wherein said other one of the electrodes isprovided with a plurality of ports for introducing said cleaning gasinto the reaction chamber.